Process of purifying crude petroleum and its distillates.



. L. EDELEANU. PROCESS FOR PURIPYING CRUDE PETROLEUM AND ITSDISTILLATES. APPLICATION TILED JUNE 1, 1908.

' 911,553. I Patented Feb.2, 1909.

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0 O O 0 O O O 0 Y L. EDELBANU. PROGES$ FOR PUBIFYING CRUDE PETROLEUM ANDITS DISTILLATES.

APPLICATION IILED JUNE 1, 1908.

Patented Feb. 2, 1909.

2 SHEETS-SHEET 2.

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All!) may UNITED STATMENT OFFICE. 7

\ LAZAR EDELEANU, OF PLOYESOlrlI, ROUMANLL' Pnocnss non Prmmyme cntmn-PETROLE M Ann, rrs msrrnpnrns.

neonatal Specification of Letters Patent.

Patented Feb. 2, 1909.

Application filed .Tune Il, 1908. Serial No. 436,042.

To all whom it mm gconcem:

- Be it-known 'that I, LAZAR EDELEANU, a

. subject of the KingofBoumania, and residing at Ployeschi, intheKingdomof Bellmania, have invented-new and usefullmprovementsinProcess'es for Purifying Crude Petroleum, its Products,-...'and itsDistillates, of which the following is a specification.-

The treatment of crude petroleum for obi taming most of its products hashitherto usu-- ally lieen carried out fractional distillation,whereup'onfthe distillateswere treated with sulfuric acid'and-alkali.This method many caseh'fiorexample, in the treat- 5 ment of petroleum,which contains large picportions of hydrocarbons poor in hydrogen, or inthe treatment of crude petroleum hav-, .ing an asphalt base or containinsulfur compounds, is unsatisfactory, but hitherto no process which wouldwork economicallyand more successfullyhas been provided to replace it.ven in-cases Where it is possible to obtain good products by using largequantities of sulfurlc acid or using a high 5 temperatureduring'refining, the recess is very costly, owing to loss from theformation of oxidized products or from other chemical action. ,The.amount of sulfuric acid re- 4 lowcr'thewost of the treatment.

40 e, Other objects will appear, from the herein- .after'de'scription. vMypresent invention consists in treating the crude. etroleum, itsdistillates and its ro'dnc'ts with liquefied sulfur dio'xid orv sul-45511111 dioxidin' the state-of liquefaction. I

. :havedis'covered that the coloring and disl agreeably smellingcompoundaand the constituents rich in carbon and cor in hydro- :gen'ofthe crude petroleum, w "ch injure the quality. of the petroleumroducts, are solu- 'ble in liquefied. sulfurous dioxid, Whereasthehydrocarbons which constitute the refined product are diflicultlysoluble oi altogether "insoluble in liquefied sulfur: 'dioxid,supposedly consisti'n principallyof'paraflins' and naphthenes. hisdiscovery "enables me to I separate: by a physical process ,theprejudicial constituents of crude petroleum of its distillates merely byusing the liquefied sulfurous dioxid as a solvent.

In. t g, F gu 1 how in r r ita section, a paratus adapted for use incarrying out t e process intermittently. Fig. 2 shows diagrammaticallyapparatus ada ted for carrying out the process continuous y.

In 1, A is a measuring tank the V crude etroleum, supplied'with acooling coil. is. another measuring tank for liquefiedsulfurous dioxid,and isv rovided with a cooling coil, both. cooling coils being suppliedwith a cooling agent through the .pi e C. G is a mixing chamber,provided WllDll an agitator g revol ved by gears, a sepafirable part ofthe contents .of which may be drawn off through the chest h -rgnrided han observation glass 0 through the pipe into the tank H, and anotherpart may be drawn ofi into the tank I. Lis acom ressor and q e y tank, it wh h is ami a gaseous sulfurous dioxid through the ct pipe], and'fromwhich liquefied su limus ioxidmay be supplied-through the pipe}? to themeasuring tankB, havingbeenquefied under moderate pressure and coolingthe usual-way. Through the same pipe ,1 gaseous sulfur dioxid may beintroduced into the measuring'tank A, through the inlet ipe and rose awhere by pressure, or by cog mg, or by acombination of ressure andcooling, the gaseousdioxid may e liquefied, an d this introduction ofgaseous sulfur dioxid is in lieu of the liquid dio'xid in the measuringtankB.

M is a ump working'the circulating system in all t e cooling coils,through the pipes 0.

(1C. This apparatus ismerely by Way of illustration, and I will nowdescribe the intermittent process of carrying out my invention by meansof this apparatus.

{1 charge tank A with crude petroleum, from which preferably. the gaseshave been distilled oil and from which more or less of the volatiles'mayor-ma'y not have been dis tilled off, or Imay chargewit with any ofthedistillates containing the coloring or illsmelling compounds or theconstituents rich in carbon and low iii-hydrogen, or those which containother undesirable constituents which are objectionable in the bestcommercial rodilcts, or with any of the products of cru e petroleum. Ichar e the tank B with liquefied sulfurous dioxi having brou ht both theoil to be treated and the lique ed sulfur-dioxid preferably to about thetemperature of ten degrees below zero. I may introduce gaseous sulfurdioxid through the pipe Z, directly into the "measuring tank A. Ihe oilcontained in the tank A is then discharged through the pipe at into themixing chamber G, where if necessary, a further cooling is effected byuse of its cooling jacket. Then the liquid sulfur dioxid is led into themixing chamber G through the inlet pipe 6, where it is thoroughly mixedby the agitator g. After the mixing has beenefiected by the agitator,which may be in perhaps five minutes or may require hours, according tothe mobility of the liquid and the quantity 1 treated, the solution ofthe injurious or undesirable constituents may be complete.

Since the. specific gravity of the liquefied sulfur dioxid is abouttwice that of therefined product, and since the liquefied sulfur dioxidcontains in solution the undesirable constituents of the crude oil orother mate rials treated, I obtained a complete separation of therefined product from the undesirable products in'solution by allowingthe contents of the mixing chamber G tosettle. At this state of theprocess, I obtain in G two distinct layers of the contents, the upperlayer being the refined product, and the lower the heavier. liquefiedsulfur dioxid withall the remaining constituents of the oil, in solutiontherein. Thereupon, I draw off the lower layer into the tank I and therefined product into the tank H. The recovery of the entire quantity ofsulfur dioxid employed may be effected by gasifying it, by relieving thepressure, whereupon it eva crates, and thegasification may be assisted ythe use of an exhaust pump, or I may employ-some heat. The last tracesof the sulfur dioxid in both the refined product and in the residuum maybe separated by washing with water or with aqueous alkaline solutions,or after the separation, I mayrecover the sulfur dioxid by taking it upin water, then boiling it off from the water, and then returning. thegaseous sulfur dioxid to the compressing pump, from which aftercompression anew it may participate in repeated operations of the samekind.

I obtain by my present invention on the one hand, products purer thanthose. ob-' tained by the ordinary refining processes by sulfuric acid;and on the otherv hand, the

residuum which, mixed with acid, was

hitherto a waste product, or partially my process obtained in comusualtreatment with sulfuric acid. The

extracted substances may be utilized any required way, for example, forobtaining therefrom aromatic compounds or other small 'the one liquidthrough the other.

4 of-the liquefied sulfur dioxi ing, then mixing the sparated purifieddis 'tillate with a further one part by weight of materials of technicalvalue, or they may be used as solvents. I may add the .whole quantity ofliquefiedsulfur dioxid at once to the substance. to be treated, or inseveral portions, dividing the treatment-into several successiveoperations, with successively portions of clean liquefied sulfur dioxid.

The treatment with a liquefied sulfur dioxid according to' my inventionmay be carried out either in closed or 0 )en vessels. If it be carriedout in open'vessels the li uid mixture should be kept at 'a'sufiicientlyow temperature to avoid eva oration of, the sulfur dioxid, say at tencegrees C. below zero. If that temperature be not sufiiciently low atthe beginning of the operation, partial evaporation of the liquefiedsulfur dioxid takes place and causes the necessary lowering of-thetemperature. Or the rocess maybe carried out by gradually addingliquefied sulfur dioxid to the cooled petroleum or petroleum products ordistillates and mixing by agitation, or the contact of the liquids maybe effected by conducting them in opposite streams against each other orby forcing Or the process may be carried out. by introducing gaseousdioxid under pressure .into the etroleum or petroleum products ordistilates and cooling the mixture, but the ressure" and the temperaturemust be re u ated so as to cause the formation of liqui sulfur dioxid;for example, at atmospheric pressure if the temperature be 10 degrees C.below zero, the solu ion of the injurious substances in the liquefiedsulfur dioxid is so arated and collects at the bottom, while thepurified roducts collect above. But I may work at igher temperatures, atthe ordinary room temperatures, by raising the pressure and workm in aclosed tank, and thereby keep the su furous dioxid in liquefied state,but it is preferable to cool the entire mixture down to about tendegrees C. below zero, more or less,'in order to get a good separation.The proportion of the liquefied sulfur dioxid depends on the amount ofthe prejudicial matter present in the crude petroleum products or itsdistillates, and on the )rop erties of the petroleum to be treate ;v forexample, four parts by weight of a distillate from Bustenari petroleumof a specific gravity ofll820- are treated with five parts by weight ofliquefied sulfur dioxid at 10 degrees C. below zero, in three stagesmixing the distillate first withthree arts by weight (i? thenseparatliquefied sulfur dioxid, then separatin again; then mixing thissecond separator and purified distillate with a further one part byweight of liquefied sulfur dioxid, and

finally separating a third time. In this way there is obtained a goodburning oil of a specific gravity of from 0.802 to 0.803. The specificavity of the substances extracted by solution by means of the liquefiedsulfur dloxid is about 0.860. The s ecific gravity of the mixture ofliquefied sul r dioxid and the dissolved contents is between 1.15 andAccording totlie specific gravity of the petroleum or petroleum productsor dis ,tillates, theircomposition, the amount and composition of theinjurious -substances and i the way in which the sulfur dioxid is added,

' the amount of sulfur 'dioxid required for uantity of dioxid forexample, if I-- am satisi ed to obtain a poorer ads of oil,'I may usethis less quant ty; if use, too small a quantity I may get no se arationat all.

have described by way of illustration an intermittent process, butobviously I may employ a continuousprocess by discharging the contentsof the mixing chamber G into along horizontal tank with separatingpartitions in the bottom, into which the mixture is introduced in avcontinuous small stream and the separatedcontents drawn offcontinuously in small streams, the purified product from the top, andthe liquid sulfur dioxid from thebottom containing in solution otherconstituents to be separated out,

"These, may be separatel for the purpose'of' expe lingth'e last tracesorit may be done by wash 'in'g or otherwise. i

then separating the principal 'bulk of the sTxlfur dioxid 'by removingthe pressure, thereby producing'evaporation, whereupon I get theseparated products with only traces of sulfur dioxid and the refinedprodnot also with traces of sulfur dioxid. treated with heat ofsulfurdioxid,

have showninIFig. 2 (if the drawing, an

apparatus adapted for carrying out the proc ess continuously. In theuse-of this apparatus the crude petroleum isplaced in the storagetank 1. "From here it flows throu h the pipe 2 into the floatcontrolled'supp y tank 3 and passes thence through the pipe 4 into thecoil 5 in the vessel 5. 'The'vessel 5 contains liquid sulfur dioxidwhich is permitted to evaporate, and by evaporating cools the petroleumwhich flows through pipes immersed in it. The cooled petroleum assesthrough the pipe 6 into the vessel 7. n this vessel 7, the petroleum ismixedwith the liquefied sulfur-dioxid which flows fromevaporator-5through the pipe 7. After the mixture has been stirred bythe agitator 8,

it flows into vessel 9 where a separation of the layers is effected. Theupper layer 10 is the petroleum from which the constituents soluble inliquid sulfur-dioxid have been removed. The lower layer 11 is thesolution of the constituents of the petroleum to be removed, in solutionin liquid sulfur-dioxid. After the separation of the layers has takenplace, the lower layer passes through pipe 12 into eva orator 5, wherethe sulfur-dioxid is remove by eva oration and passes through pipe 13into t e com ressor 14 and is again condensed into liqui sulfur-dioxid.This condensation takes 'place in the con denser 15 into which thesulfur-dioxid passes through pipe 16 from the compressor. The

liquefied sulfur dioxid passes out of the condenser 15 throu h pipe 17again into the eva orator 5 an then returns tothe mixer 7 t rou h pipe 7The hydrocarbons extracted rom the principal mass of the sulfurdioxidflow out of the evaporator 5 through pipe 18 under the action of pum 19and pass through pipe 19 into the'tal tank 20 rovided with bafiie plates20 and are here .ireed by'further evaporation from any sulfurdioxidwhich may still be resent induced by the pump 23. The en fur-dioxidthusevaporated passes through pipe 21 into pipe '22 leading to pump 23, andis conveyed to the the condenser through pipe 23*. The upper layer ofliquid, 10 is drawn out of the vessel 9 through pipe 24"by the actionof-pump 25 andpasses through pi e26 into a tall tank 27L rovidged withba e plates 27 a where it is i ieed from any remaining sulfur-dioxidwhich may be present indficed by the pump 23. This sulfur-dioxid passesthrough pipe 28 into pipe 22 and thus reaches the conpressor 23. Thepower necessary to work the apparatus is provided by the. steam engine29, which receives steam through pipe 30. The exhaust steam passesthrough pipe 31 to heat the tall tanks 20 and 27, by meansof theradiators 20 and 27 b shown in dotted lines within said tanks. The steampump 32 likewise receives steam through pipe 30 and conveys to thecondenser 15, the water obtained through pipe 34.

I The present process is suitable for all kinds of crude petroleum, itsproducts,'and its distillates, es eci'ally isit used for refining Texas,Ohio, Ca ifornia, Roumania, Galicia and similar oils. good oils burningwithout smoke, with good illuminating power and of good merchantablequality.

' The chief advantages of the present invention are the emplo ment of acheap solvent, the sulfur-dioxi which may be produced by burning sulfur,or by roasting pyrites, or by heating sludge sulfuric acid obtained bythe ordinary process of refining petroleum; no loss in the treatedmaterial either by oxidation or by other chemical re- It is possible toobtain action; the entire quantity of the solvent can be recovered andused again, and the absorption of heat by the evaporation of the liquiddioxid can be utilized to 'cool down to the required temperature theprodnets to be treated.

Thus it will be seen that my invention is comprehensive and extends toevery application of solubility to separate the constitucuts of crudeoil or of any of its products or distillates by sulfur-dioxid, whichdissolves one or more of those constituents and refuses to dissolveothers, whatever the apparatus used, whether the process is intermittentor continuous, whatever the succession or order of the various steps,whether sulfur-dioxid is introduced in a state of liquefaction, or. is.liquefied during the process, whatever the time of treatment or theproportion of the sulfur-dioxid, and whether in closed or open vessels,provided it be in suiiicient quantity to dissolve some or all of theingredients of the oil treated, and not in such small quantity as toprecipitate.

Having now described my invention, what I claim as new, and desire tosecure by Letters Patent is:

'1. The process of treating petroleum, pctroleum products and thedistillates, which consists in treating the same with liquefiedsulfur-dioxid, in quantity sufficient to dissolve constituents to beseparated, dissolving constituents of the same therein, and separatingthe two liquids.

2. The process of purifying petroleum, petroleum products and thedistillates, which consists in treating the same with liquefiedsulfur-dioxid, in quantity suflicient to dissolve constituents to beseparated, separating the two liquids,f "and separating thesulfur-dioxid both from the purified petroleum and from the dissolvedconstituents.

3. The process of treating petroleum, its products and distillates,which consists in introducing gaseous sulfur-dioxid into the material tobe treated in sufiicient quantity.

to dissolve the constituents to be removed, reducing the sulfur-dioxidto a liquid state whereby the said constituents will dissolve therein,and separating the resulting liquids.

4E. The process of treating petroleum, petroleum products, and thedistillates, which consists in introducing gaseous sulfur-dioxid intothe substances to be treated, in sufiicient quantities to dissolve theconstituents to be removed under pressure suflicient at the working temerature to liquefy the gas, and separating t 1e two liquids by loweringthe temperature of the mixture,

5. The process of treating petroleum, petroleum products and thedistillates, which consists in introducing gaseous sulfur-dioxid in suchquantity as to dissolve those hydrocarbons which are rich in carbon andlow in hydrogen, cooling the mixture to a tem crature below zerocentigrade, whercby 516 sulfur-dioxid is liquefied wherein thehydrocarbons rich in carbon and poor in hydrogen are dissolved, andcausing the mixture to separate in two liquids, the lighter containingthe purified constituents, and the heavier containing the liquefiedsulfur-dioxid and dissolved hydrocarbons, and drawing oil the two layersseparately.

6. The process of treating petroleum, petroleum products and thedistillates, for the separation of the heavy hydrocarbons, rich incarbon, which consists in treating them with liquefied sulfur-dioxid insuch quantity that the said hydrocarbons are dissolved in the liquefiedsulfur-dioxid, then causing separation of the treated material, anddrawing off the liquids separately.

7. The process of treating petroleum, petroleum products and itsdistillates, which consists in treating the same with sulfurdioxid insufiicient quantitvto dissolve the constituents to be removed,dissolving con stituents of the same therein, applying pressure andseparating the two liquids.

8. The process of treating petroleum, petroleum products and thedistillates, which consists in treating the same with sulfurdioxid insufficient quantity to dissolve the constituents to be removed,dissolving constituents of the same therein, gradually cooling theliquids and separating and. drawing oii' the liquids by stages.

' 9. The process of treating petroleum, petroleum products, and thedistillates, which consists in treating the same with sulfur dioxid insuflicient quantity to dissolve the constituents to be removed,dissolving constituents of the same therein, conducting a stage oftheprocess under cold and pressure, and separating the li uids.

In witness whereof my hand in presence of two-witnesses.

LAZAR EDELEANU. Witnesses: I

HENRY HAsrER, VVOLDEMAR HAUPT.

have hereunto set

